CN107670689A - A kind of silicoaluminophosphamolecular molecular sieves, synthesis and its application of metal substitution - Google Patents
A kind of silicoaluminophosphamolecular molecular sieves, synthesis and its application of metal substitution Download PDFInfo
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- CN107670689A CN107670689A CN201710994744.3A CN201710994744A CN107670689A CN 107670689 A CN107670689 A CN 107670689A CN 201710994744 A CN201710994744 A CN 201710994744A CN 107670689 A CN107670689 A CN 107670689A
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- China
- Prior art keywords
- molecular sieve
- sapo
- crystallization
- silicoaluminophosphamolecular molecular
- molecular sieves
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 58
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 36
- 239000002184 metal Substances 0.000 title claims abstract description 33
- 230000015572 biosynthetic process Effects 0.000 title abstract description 14
- 238000003786 synthesis reaction Methods 0.000 title abstract description 14
- 238000006467 substitution reaction Methods 0.000 title abstract description 10
- 238000002425 crystallisation Methods 0.000 claims abstract description 31
- 230000008025 crystallization Effects 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000010703 silicon Substances 0.000 claims abstract description 18
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 13
- 229910052718 tin Inorganic materials 0.000 claims abstract description 11
- 239000011574 phosphorus Substances 0.000 claims abstract description 9
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 8
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 6
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 43
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 10
- 229910001868 water Inorganic materials 0.000 claims description 10
- 235000011007 phosphoric acid Nutrition 0.000 claims description 9
- -1 alkyl silicate Chemical compound 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 238000010189 synthetic method Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Natural products CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 4
- 229910001593 boehmite Inorganic materials 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N methyl monoether Natural products COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 230000003068 static effect Effects 0.000 claims description 4
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 4
- 206010013786 Dry skin Diseases 0.000 claims description 3
- 239000003292 glue Substances 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000012452 mother liquor Substances 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical group [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 229940043237 diethanolamine Drugs 0.000 claims description 2
- 229940043279 diisopropylamine Drugs 0.000 claims description 2
- 238000009415 formwork Methods 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 2
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 claims 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- 239000012266 salt solution Substances 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 16
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 12
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 7
- 230000008859 change Effects 0.000 description 7
- 241000269350 Anura Species 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- 239000003245 coal Substances 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 1
- 229910017119 AlPO Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- GIWFEJPOFMJBNN-UHFFFAOYSA-N [Sn].OCS(=O)(=O)O Chemical compound [Sn].OCS(=O)(=O)O GIWFEJPOFMJBNN-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- FNIHDXPFFIOGKL-UHFFFAOYSA-N disodium;dioxido(oxo)germane Chemical compound [Na+].[Na+].[O-][Ge]([O-])=O FNIHDXPFFIOGKL-UHFFFAOYSA-N 0.000 description 1
- TVQLLNFANZSCGY-UHFFFAOYSA-N disodium;dioxido(oxo)tin Chemical compound [Na+].[Na+].[O-][Sn]([O-])=O TVQLLNFANZSCGY-UHFFFAOYSA-N 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- DPJBJAPWEDZODW-UHFFFAOYSA-N ethanesulfonic acid;tin Chemical compound [Sn].CCS(O)(=O)=O DPJBJAPWEDZODW-UHFFFAOYSA-N 0.000 description 1
- KGCUHDFXFXQDNT-UHFFFAOYSA-N ethanol;germanium Chemical group [Ge].CCO KGCUHDFXFXQDNT-UHFFFAOYSA-N 0.000 description 1
- UARGAUQGVANXCB-UHFFFAOYSA-N ethanol;zirconium Chemical compound [Zr].CCO.CCO.CCO.CCO UARGAUQGVANXCB-UHFFFAOYSA-N 0.000 description 1
- 125000000816 ethylene group Chemical class [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- HZHXGUXTFHBONU-UHFFFAOYSA-N formic acid;zirconium Chemical compound [Zr].OC=O HZHXGUXTFHBONU-UHFFFAOYSA-N 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- UTEFBSAVJNEPTR-RGEXLXHISA-N loprazolam Chemical compound C1CN(C)CCN1\C=C/1C(=O)N2C3=CC=C([N+]([O-])=O)C=C3C(C=3C(=CC=CC=3)Cl)=NCC2=N\1 UTEFBSAVJNEPTR-RGEXLXHISA-N 0.000 description 1
- 229960003019 loprazolam Drugs 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- HNDXKIMMSFCCFW-UHFFFAOYSA-N propane-2-sulphonic acid Chemical class CC(C)S(O)(=O)=O HNDXKIMMSFCCFW-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229940079864 sodium stannate Drugs 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium(II) oxide Chemical compound [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/54—Phosphates, e.g. APO or SAPO compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
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Abstract
The invention discloses a kind of silicoaluminophosphamolecular molecular sieve catalyst of the substitution containing tetravalent metal, the substituted metallic element (Me) of sial is including Ti, Zr, Sn, Ge, Hf, Nb etc. in framework of molecular sieve, it is preferred that Ti, Zr, Sn, Ge, further preferred Ti, Zr.The present invention first prepares Primogel burin-in process at moderate temperatures, is then supplemented silicon source and phosphorus source and forms crystallization predecessor, using divide temperature section crystallization synthesis MeSAPO n (n=5,11,17,18,34,35,44,56) molecular sieve, preferably synthetic MeSAPO 34.The present invention seeks to insert metallic atom in silicoaluminophosphamolecular molecular sieves skeleton, modulation silicoaluminophosphamolecular molecular sieves acid centre property, the carbon distribution that oxygenatedchemicals is changed into low-carbon alkene reaction is reduced, extends its catalyst life, and the yield of low-carbon alkene is improved, particularly increase the yield of ethene.
Description
Technical field
Changed into the present invention relates to a kind of silicoaluminophosphamolecular molecular sieves of tetravalent metal substitution, synthesis and its in oxygenatedchemicals
Application in low-carbon alkene, belongs to technical field of molecular sieve.
Background technology
Oxygenatedchemicals changes into low-carbon alkene reaction at present, mainly using coal-based methanol olefin process as typical reaction,
I.e. using coal as raw material, through coal gasification preparing synthetic gas, synthesising gas systeming carbinol, then to preparing light olefins from methanol, separation of olefins and
The process of polymerization.Wherein methanol-to-olefins (MTO) are the cores of the technology, are development non-oil resource production ethene, propylene etc.
The core technology of product.It is in short supply for alleviating petroleum resources, realize that the clean and effective of coal utilizes, there is important strategy meaning
Justice.
SAPO molecular sieve has A1O4, SiO4 and PO4 tetrahedral network connected by oxygen atom, duct in crystal, because
Si4+Substitute P5+Or A13+It is caused acid or substituted with metal and producing acidity makes the molecular sieve play important work in MTO catalysis
With.In SAPO catalyst series, SAPO-34 shows prominent superiority, low-carbon in the reaction of preparing olefin by conversion of methanol
Olefine selective is up to 90%, C5Above product and branched chain isomer thing are seldom.Due to SAPO-34 have special pore passage structure and
Bronsted acidity, when being reacted for catalysis methanol alkene (MTO), the gaseous products of methanol conversion only have C1~C5 hydro carbons, its
Octatomic ring aperture forms larger diffusional resistance to macromolecular, and having C2 and C3 hydro carbons only easily can diffuse out outside crystal.
In addition, the larger hydrocarbon of relative molecular mass is tended to generate in acid too strong acid site, and moderate strength possessed by SAPO-34
Acid site, limit the further reaction of ethene, propylene, SAPO-34 is shown in the reaction of preparing olefin by conversion of methanol
Prominent superiority, selectivity of light olefin are up to 90%.
The structure and number of the intensity in acid site and number and framework silicon atom are closely related in framework of molecular sieve
(J.Phys.Chem, 1997,101,5249-5262), i.e. SAPO molecular sieve skeleton silicone content and coordination environment have to its acidity
There is strong influence.For SAPO-34 molecular sieve catalysts, the intensity of acid centre and number directly affect in framework of molecular sieve
The MTO catalytic performances of SAPO-34 molecular sieves, acid stronger acid centre are beneficial to the generation of alkane molecule, acid weaker acid
Then there is a possibility that methanol can not convert completely, the acid centre of moderate strength can limit the generation of alkane and aromatic hydrocarbons at property center,
Be advantageous to improve the selectivity of the low-carbon alkene such as ethene and propylene.
It is generally acknowledged that the crystallization process of SAPO molecular sieve analogs follow silicon substitution mechanism (J.Phys.Chem., 1994,98,
4878-4883；J.Phys.Chem., AlPO molecular sieves 1994,98,9614-9618), are firstly generated, silicon atom is taken by the isomorphous
The mode in generation enters framework of molecular sieve, and its substitution mode has two kinds：(1) Si substitutes P；(2) 2Si substitutes P+Al.For SAPO-34
Molecular sieve, silicone content will influence synthesis SAPO-34 framework of molecular sieve Si coordination environment in gel, in the relatively low situation of silicone content
Under, SAPO-34 synthesis is carried out in a manner of silicon individually substitutes skeleton phosphorus atoms, generates Si (4Al) structure；And high silicon content
When, then there is the second way i.e. 2Si while substitute the mode of a pair of Al+P atoms to cooperate with progress, form Si (3Al), Si (2Al),
A variety of silicon structural units such as Si (1Al), Si (0Al).The result of silicon substitution phosphorus is to produce negative skeleton electric charge, forms some strength
B acid sites；Silicon substitutes the mode of a pair of phosphorus aluminium atoms simultaneously, can form the distribution of a variety of skeleton electric charges, is formed different strong
The B acid sites of degree.
Patent CN1704390 is modified to obtain Zn-SAPO-34 molecular sieves by using metallic element Zn to SAPO-34,
And as the catalyst of methanol-to-olefins, the reaction generation low-carbon alkene under suitable reaction condition.Due to metallic element
Zn addition influences to caused by SAPO-34 skeleton and pore structure, improves selectivity of the molecular sieve to low-carbon alkene.
Transiting state metal same order elements, which are entered in AlPO4 or SAPO skeletons, normally results in new acidic site generation, because
And change the acidity of main material.Because acidity influences activity, metal substitution is an easy method, can control or change
Become the characteristic of the catalyst in MTO techniques.In the small pore molecular sieve that different metal is modified, NiSAPO-34 receives maximum
Concern, because this catalyst shows the selectivity high to ethene.
Mentioned in document ((2003) 203-218 of Fuel Processing Technology 83), in order to improve ethene
Selectivity is, it is necessary to make great efforts to carry out materialization modification to small pore molecular sieve material.Such as W metal is added to by same order elements
In SAPO-34 framework of molecular sieve, the selectivity that can improve ethene in MTO techniques is found that.This is due to after inserting Ni
The deformation of SAPO-34 framework of molecular sieve and the change of acidic site.Show that Ni ions are located in several characterization results of this material
The frame position of four-coordination.The outer proton of the skeleton of loosel bound is considered as the pass that catalyst methanol is converted into ethene high selectivity
Key component.Also some report be on CoSAPO-34 and MnSAPO-34 methanol convert.
Document (Studies in Surface Science and Catalysis, 147,2004,445-450) shows gold
The insertion of category ion has a great impact to the structure and acidity of molecular sieve.Most MeASPO-34 molecular sieves show that MTO performances have
The raising of effect improves.Particularly Co2+、Zn2+And Mg2+The insertion display of ion has good improvement to make to MTO catalyst performance
With.
In MTO catalytic reactions, the larger product of volume is easily formed in SAPO-34 molecular sieve outer surfaces and cage and duct
Carbons material, easily cause the inactivation of catalyst.The generating rate of carbon distribution class material is thus efficiently reduced, and then extends catalysis
Agent catalytic life, the catalytic performance for improving catalyst are extremely important.SAPO synthesized by existing literature and patent
Molecular sieve analog even can not extremely significantly improve the selectivity of low-carbon alkene especially ethene, and effectively extend the catalyst longevity
Life.The present invention provides a kind of synthetic method of the silicoaluminophosphamolecular molecular sieves of tetravalent metal substitution, prepared MeSAPO-34 molecules
Sieve catalyst will efficiently solve subject matter in MTO catalytic reactions.
The content of the invention
The present invention provides a kind of silicoaluminophosphamolecular molecular sieves of tetravalent metal substitution and its synthetic method, this molecular sieve both may be used
Molecular sieve catalyst surface acidity can be adjusted with modulation pore passage structure again, Reaction-diffusion terms path is reduced, reduce crystalline solid surface
The concentration of Si atoms, the concentration for reducing acid, so as to regulate and control the proportion of composing of low-carbon alkene in MTO reaction products, are particularly improved
The yield of ethene.
The present invention provides a kind of silicoaluminophosphamolecular molecular sieve catalyst containing metal, contains tetravalent metal member in framework of molecular sieve
Element, Si, Al, P and Me (tetravalent metal) are respectively according to corresponding oxide component molar ratio in framework of molecular sieve structure：
nSiO2：nAl2O3：n P2O5：nMeO2=0.01~1.0：1.0：0.5~1.5：0.001~2.0.
Further, in the above-mentioned technical solutions, described silicoaluminophosphamolecular molecular sieves are SAPO-5, SAPO-11, SAPO-
17th, it is a kind of in SAPO-18, SAPO-34, SAPO-35, SAPO-44, SAPO-56, preferably SAPO-34.
Further, in the above-mentioned technical solutions, in the skeleton of silicoaluminophosphamolecular molecular sieves containing tetravalent metal of the present invention,
Tetravalent metal is a kind of in Ti, Zr, Sn, Hf, Nb, Ge, preferably Ti, Zr, Sn, Ge, further preferred Ti, Zr metal.
Further, in the above-mentioned technical solutions, the skeleton of silicoaluminophosphamolecular molecular sieves containing tetravalent metal knot of the present invention
Si, Al, P and Me (metal) are preferably respectively according to corresponding oxide component molar ratio in structure：nSiO2：nAl2O3：n P2O5：
nMeO2=0.05~0.5：1.0：0.5~1.5：0.01~0.5.
The present invention provides the above-mentioned synthetic method of silicoaluminophosphamolecular molecular sieves containing tetravalent metal and comprised the following steps：
(1) first silicon source, silicon source, organic formwork agent and water are well mixed, then add phosphorus source, it is to be mixed uniformly after again plus
Enter tetravalent metal salting liquid, be sufficiently stirred at room temperature~80 DEG C 0.5~10 hour, then static burn in is anti-in 80~100 DEG C
Answer 4.0~24.0 hours；
(2) it is supplemented adding silicon source and phosphorus source into the mixed solution after step (1) aging, crystallization is obtained after stirring completely
Precursor mixture, it is fitted into hydrothermal reaction kettle and is divided to two sections of temperature crystallization, first paragraph is 125~170 DEG C, and second segment is 170~200
DEG C, room temperature is cooled to after the completion of crystallization and stops crystallization, solid crystallized product is separated with mother liquor, product is washed to neutrality,
105~130 DEG C of dryings, 450~650 DEG C are calcined in atmosphere, obtain the silicoaluminophosphamolecular molecular sieves original powder of the metal containing four-coordination.
Further, in the above-mentioned technical solutions, in crystallization precursor mixture of the present invention each component mol ratio
For：
nSiO2：nAl2O3：n P2O5：nMeO2：nOSDA：nH2O=0.1~0.2：1.0：1.0~5.0：0.01~0.05：
0.05~5.0：10~50.
Further, in the above-mentioned technical solutions, the Crystallization of Zeolite mode is dynamic crystallization or static crystallization, preferably
Dynamic crystallization mode.
Further, in the above-mentioned technical solutions, silicon source of the present invention be white carbon, active silica, Ludox,
One or more of mixtures of alkyl silicate；Silicon source is aluminium isopropoxide, alumina gel, Alumina gel, SB powder, boehmite, hydrogen-oxygen
Change aluminium, one or more of mixtures of boehmite；Phosphorus source is orthophosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, organic phosphatization
One or more in thing or phosphorous oxides；Template be diethylamine, triethylamine, morpholine, n-propylamine, isopropylamine, di-n-propylamine,
Diisopropylamine, tripropyl amine (TPA), n-butylamine, isobutyl amine, monoethanolamine, diethanol amine, triethanolamine, cyclohexylamine, TMAH,
One kind or any several mixtures in tetraethyl ammonium hydroxide, TPAOH or TBAH.
Further, in the above-mentioned technical solutions, titanium source selection fluotitanic acid (H of the present invention2TiF6), titanium sulfate, sulfuric acid
One or more in oxygen titanium, titanium tetrachloride, titanium trichloride, butyl titanate.
Further, in the above-mentioned technical solutions, zirconium source of the present invention be selected from zirconium oxide, zirconyl chloride, zirconyl nitrate,
It is one or more in zirconium sulfate, formic acid zirconium, zirconium acetate, ethanol zirconium, propyl alcohol zirconium.
Further, in the above-mentioned technical solutions, tin source of the present invention is selected from Loprazolam tin, ethane sulfonic acid tin, third
Alkyl sulfonic acid tin, 2- propane sulfonic acids tin, hydroxy methane sulfonic acid tin, 2- hydroxyethyl -1- sulfonic acid tin, 2- hydroxybutyl -1- sulfonic acid tin,
Any one in sodium stannate.
Further, in the above-mentioned technical solutions, ge source of the present invention from germanium oxide, germanium alkoxide, germanium chloride and/or
Sodium germanate one of which or it is several be mixed by any ratio, wherein germanium alkoxide is ethanol germanium or germanium chloride.
The present invention provides the application of the above-mentioned silicoaluminophosphamolecular molecular sieves containing tetravalent metal, is used to convert oxygen as catalyst
Compound is prepared in low-carbon alkene reaction.
Further, in the above-mentioned technical solutions, conversion oxygenate of the present invention is methanol, ethanol, methyl ether, diformazan
In ether any one, the mixture that is mixed with arbitrary proportion of two kinds and the above.
Further, in the above-mentioned technical solutions, any one in the preferred methanol of oxygenatedchemicals, dimethyl ether or with any
The mixture of ratio mixing.
Further, in the above-mentioned technical solutions, reaction condition of the present invention is：380~550 DEG C of reaction temperature, instead
Answer 0.1~0.4MPa of pressure, 0.3~10h of weight (hourly) space velocity (WHSV) of methanol-1。
The method that the present invention improves hetero atom same order elements degree, and by screening the Organic amine template of different spaces structure
Agent, synthesize MeSAPO-34 molecular sieves so as to controllable.
Molecular sieve catalyst provided by the present invention shows the catalytic activity of superelevation, and its catalytic life is traditional SAPO-
More than 2 times of 34 molecular sieve catalysts, the total recovery of ethene and propylene reach more than 87%, the mol ratio of ethylene/propene selectivity
More than 1.60.
Brief description of the drawings
Below in conjunction with the accompanying drawings and embodiment the invention will be further described：
Fig. 1 is the TiSAPO-34 sieve sample XRDs synthesized in embodiment 1；
Fig. 2 is the ZrSAPO-34 sieve sample XRDs synthesized in embodiment 9；
Fig. 3 is the SAPO-34 sieve sample XRDs synthesized in comparative example 1；
Fig. 4 is the TiSAPO-34 sieve samples SEM figures synthesized in embodiment 1；
Fig. 5 is the ZrSAPO-34 sieve samples SEM figures synthesized in embodiment 9；
Fig. 6 is the SAPO-34 sieve samples SEM figures synthesized in comparative example 1.
Embodiment
Embodiment of the present invention and caused effect, but the guarantor of the present invention are further illustrated by embodiment and comparative example
Shield scope is not limited to the content listed by embodiment.
Embodiment 1
(1) first by 247.61g boehmites (78.24wt%), 128.22g Ludox (SiO2：26.71wt%),
385.88g triethylamines (99wt%), 437.99g orthophosphoric acid (85wt%) and 299.27g water are small in 25 DEG C of processing 2 after mixing
When, it is to be mixed uniformly after 21.55g butyl titanates (99wt%) are added dropwise again, be sufficiently stirred at 40 DEG C 4 hours, then at 100 DEG C
Middle static burn in is reacted 6 hours；
(2) be supplemented into the mixed solution after step (1) aging add 162.49g boehmites (78.24wt%),
182.68g orthophosphoric acid (85wt%) and 273.90g water, the mol ratio of corresponding each component are：SiO2：Al2O3：P2O5：TiO2：
OSDA：H2O=0.181：1.0：0.856：0.02：1.20：15.Gel after stirring completely, which is fitted into hydrothermal reaction kettle, is divided to two sections
Temperature crystallization 60rpm speed dynamics, first paragraph are 150 DEG C of crystallization 12 hours, and second segment is 190 DEG C of crystallization 30 hours, and crystallization is anti-
Should after the completion of it is sudden be as cold as room temperature stop crystallization, solid crystallized product is separated with mother liquor, product be washed with deionized repeatedly to
Neutrality, 105 DEG C of dryings 12 hours, 550 DEG C are calcined 4 hours in Muffle furnace, obtain TiSAPO-34 molecular screen primary powders.Sample is designated as
A, its XRD diffraction pattern as shown in figure 1, ESEM (SEM) picture as indicated at 3.
Embodiment 2~10
Synthesis step similar to Example 1, the difference is that synthesis material, aging temperature, ageing time, crystallization temperature are brilliant
Change time difference, synthesis material species is as shown in table 1, the proportioning of each component and the synthesis condition such as institute of table 2 in crystallization predecessor
Show, sample is designated as B~J respectively.What embodiment 2~8 synthesized is TiSAPO-34 molecular sieves, and what embodiment 9~10 synthesized is
ZrSAPO-34 molecular sieves
Table 1
Table 2
Comparative example 1
Weigh 7.0g dry glue powders to be dissolved in 10.0g deionized waters, be stirring evenly and then adding into template 29.8g tetraethyl hydrogen-oxygens
Change ammonium (25wt%) and continue to stir.Pure 85% orthophosphoric acid 11.0g will separately be analyzed it is added in 10.0g deionized waters and is formed
Phosphoric acid solution, it is added in above-mentioned solution, stirring 2h obtains uniform collosol intermixture.By 1.5g acidic silicasols (SiO2：
30wt%) it is added to 2.6g triethylamines (99wt%) in above-mentioned collosol intermixture, it is molten is uniformly mixing to obtain initial crystallization forerunner
Glue.The additional proportion of each component：0.15SiO2：1.0A12O3：1.0P2O5：1.0TEAOH：0.5TEA：60H2O,
Then crystallization forerunner's colloidal sol is placed in 100mL closed reactors, is warming up to 180 DEG C and keeping temperature crystallization 60h,
Crystallization product is taken out when autoclave temperature is down to room temperature, centrifuges solid product, is washed with deionized water to neutrality, production
Product are placed in 110 DEG C of thermostatic drying chamber and dried 12 hours, place into Muffle furnace and are warming up to 550 DEG C of constant temperature calcining 4h and obtain
SAPO-34 sieve samples, are designated as VS-1.
Comparative example 2
1) 4.88g SB powder (72 weight %), 20g water, 7.93g phosphoric acid (85wt%), 1.6g are sequentially added into synthesis reactor
Ludox (28wt%), 10.8g triethylamines are added after stirring evenly, sealing, stirs in lower 1h and is warming up to 190 DEG C, crystallization 2h.Take out and close
Into kettle, cooling.
2) 4.88g SB powder, 29g water and 7.93g orthophosphoric acid are sequentially added into beaker, after stirring evenly, adds the second of 10.8g tri-
Amine, sealing, 30min is to uniform for stirring, then adds after cooling above in synthesis reactor.
3) the synthesis reactor sealing after feeding, stir and be warming up to 200 DEG C in lower 2h, after crystallization 20h, solid product is through centrifugation point
From being washed with deionized to neutrality, after 120 DEG C of air dryings, obtain SAPO-34 sieve samples, be designated as VS-2.
Comparative example 3
7.068 boehmites (are contained into Al2O3：72.2wt%) it is dissolved in 19ml deionized waters, stirs lower addition 4.8g
Ludox (SiO2：25wt%), 11.53g orthophosphoric acid (concentration 85wt%) is slow added into, adds water 10ml, continues 10 points of stirring
Clock, then add 1.07g Zr (NO3)4·H2O (99wt%) and 10ml water, continue stirring 20 minutes, add the second of 15.15g tri-
Amine (NEt3) well mixed, its gel composition is:3NEt3:0.4SiO2:A12O3:P2O5:0.05ZrO2：50H2O。
Said mixture material is moved into stainless steel synthesis reactor and sealed, crystallization 24 hours under 200 DEG C and self-generated pressure, Gu
Body product deionised water is ZrAPSO-34 molecular sieves after 100 DEG C of air dryings, is designated as VS-3 to neutrality.
Embodiment 11
The evaluation of catalyst：By TiSAPO-34, ZrSAPO-34 molecular sieve and comparative example resulting in embodiment 1~10
1~2 obtained SAPO-34 sieve samples carry out tabletting, are crushed to 20~40 mesh.Weigh 1.0g samples and load fixed bed reaction
Device, carry out MTO evaluations.Lead to nitrogen activation at 500 DEG C 1.5 hours, be then cooled to 450 DEG C.Methanol is carried by nitrogen, nitrogen
Flow velocity is 15ml/min, methanol weight air speed 4.0h-1.Resulting product is carried out by online gas-chromatography (Agilent7890)
Analysis, the results are shown in Table 5.From which it can be seen that compared with comparative example, 8 embodiment samples are respectively provided with the high catalysis longevity
Life, at the same the total recovery of ethene and propylene exceeded 87.0%, MTO reaction life-span it is also longer.
Table 3
t50：Conversion ratio was reduced to for 50% time undergone from 100%；t98：Conversion ratio is reduced to 98% institute from 100%
The time of experience.
As can be seen from Table 3, TiSAPO-34 the and ZrSAPO-34 molecular sieve catalysts that prepared by method provided by the invention
In MTO reactions, there is higher low-carbon alkene (C2 =+C3 =) selectivity reachable more than 87%, ethylene/propene (C2=/C3 =)
Selective ratio be more than 1.7, and the conversion life-span that conversion ratio drops to before 50% more than 18 hours, illustrate the present invention provide
TiSAPO-34 and ZrSAPO-34 molecular sieve catalysts there is the selectivity of MTO reacting ethylenes and good life-span.
The embodiment only technical concepts and features to illustrate the invention, its object is to allow person skilled in the art
Scholar can understand present disclosure and implement according to this, and it is not intended to limit the scope of the present invention.It is all according to the present invention
The equivalent change or modification that Spirit Essence is made, it should all be included within the scope of the present invention.
Claims (9)
1. a kind of silicoaluminophosphamolecular molecular sieve catalyst containing metal, it is characterised in that contain tetravalent metal member in framework of molecular sieve
Element, Si, Al, P and tetravalent metal Me are respectively according to corresponding oxide component molar ratio in framework of molecular sieve structure：nSiO2：
nAl2O3：n P2O5：nMeO2=0.01~1.0：1.0：0.5~1.5：0.001~2.0, tetravalent metal Me is selected in framework of molecular sieve
It is a kind of from tetravalence Ti, Zr, Sn, Hf, Nb, Ge.
2. the silicoaluminophosphamolecular molecular sieve catalyst containing metal according to claim 1, it is characterised in that silicoaluminophosphamolecular molecular sieves
It is a kind of in SAPO-5, SAPO-11, SAPO-17, SAPO-18, SAPO-34, SAPO-35, SAPO-44, SAPO-56.
3. the silicoaluminophosphamolecular molecular sieve catalyst containing metal according to claim 1, it is characterised in that in framework of molecular sieve
Si, Al, P and Me are respectively according to corresponding oxide component molar ratio：nSiO2：nAl2O3：n P2O5：nMeO2=0.05~
0.5：1.0：0.5~1.5：0.01~0.5.
4. the synthetic method of the silicoaluminophosphamolecular molecular sieve catalyst containing metal according to claim 1, it is characterised in that including
Following steps：
(1) first silicon source, silicon source, organic formwork agent and water are well mixed, then add phosphorus source, it is to be mixed uniformly after add four
Valency metal salt solution, it is sufficiently stirred at room temperature~80 DEG C 0.5~10 hour, then the static burn in reaction 4.0 in 80~100 DEG C
~24.0 hours；
(2) it is supplemented adding silicon source and phosphorus source into the mixed solution after step (1) aging, crystallization forerunner is obtained after stirring completely
Mixture, it is fitted into hydrothermal reaction kettle and is divided to two sections of temperature crystallization, first paragraph is 125~170 DEG C, and second segment is 170~200 DEG C,
Room temperature is cooled to after the completion of crystallization and stops crystallization, solid crystallized product is separated with mother liquor, product is washed to neutrality, and 105
~130 DEG C of dryings, 450~650 DEG C are calcined in atmosphere, obtain the silicoaluminophosphamolecular molecular sieves original powder of the metal containing four-coordination.
5. synthetic method according to claim 5, it is characterised in that：Silicon source is that white carbon, active silica, silicon are molten
One or more of mixtures of glue, alkyl silicate；Silicon source is aluminium isopropoxide, alumina gel, Alumina gel, SB powder, boehmite, hydrogen
One or more of mixtures of aluminum oxide, boehmite；Phosphorus source is orthophosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, organophosphor
One or more in compound or phosphorous oxides；Template is diethylamine, triethylamine, morpholine, n-propylamine, isopropylamine, two positive third
Amine, diisopropylamine, tripropyl amine (TPA), n-butylamine, isobutyl amine, monoethanolamine, diethanol amine, triethanolamine, cyclohexylamine, tetramethyl hydroxide
One kind or any several mixtures in ammonium, tetraethyl ammonium hydroxide, TPAOH or TBAH.
6. synthetic method according to claim 4, it is characterised in that：In the crystallization precursor mixture obtained in step (2)
The mol ratio of each component is：
nSiO2：nAl2O3：n P2O5：nMeO2：nOSDA：nH2O=0.1~0.2：1.0：1.0~5.0：0.01~0.05：0.05
~5.0：10~50.
7. the silicoaluminophosphamolecular molecular sieves containing tetravalent metal are used for convert oxygenate as catalyst as claimed in claim 1
Prepare the application in low-carbon alkene reaction.
8. application according to claim 7, it is characterised in that described oxygenatedchemicals is methanol, ethanol, propyl alcohol, fourth
In alcohol, methyl ether, ethyl methyl ether, dimethyl ether, diethyl ether, diisopropyl ether, dimethyl carbonate any one, two kinds and the above be with any
The mixture of ratio mixing.
9. application according to claim 8, it is characterised in that reaction condition is：380~550 DEG C of reaction temperature, reaction pressure
0.1~0.4MPa of power, 0.3~10h of weight space velocity of oxygenatedchemicals-1。
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